Patent GB-918360-A (GB)
Title: Bis-1,3-dioxolanes
IPC: C08K5/156
Filed: 1961-09-12
Abstract: Bis-1,3-dioxolanes having the formula <PICT:0918360/III/1> in which R is a tetravalent organic radical having at least 2 carbon atoms, each terminal carbon atom of the radical being a member of one dioxolane ring, and X is an organic radical comprising 2 carbon atoms in the dioxolane ring, at least one of said carbon atoms in X bearing an alkenyl substituent, are used for the production of coating compositions which can be applied and dried at room temperature or for a short time at slightly elevated temperature, e.g. 50 DEG -150 DEG C., to give hard, glossy films.  The compounds are usually mixed with metallic driers such as lead, manganese, zinc, iron, nickel, cadmium, copper, tin, zirconium and, preferably, cobalt salts. Suitable salts, for example, are acetates, naphthenates, linoleates, resinates, tallates, oxalates and phthalates.  Other additives which may be used as solvents, plasticizers, pigments, extenders, inhibitors and flow-control agents.  Other film-forming materials, such as polymers and copolymers of acrylic esters, vinyl acetate and styrene and unsaturated polyesters may also be added to the compositions.  Examples are given of the preparation of coating compositions by mixing (a) the compound of formula <PICT:0918360/III/2> with (i) cobalt butyl phthalate solution to give a clear hard film at room temperature in a few days and at 110 DEG C. in 20 mins. and (ii) with titanium dioxide, toluene and cobalt butyl phthalate to give a coating composition which could be sprayed on glass ceramics, wood and metal; (b) a compound of the general formula given above, in which R is <FORM:0918360/III/1> and X is <FORM:0918360/III/2> is mixed with 1% of cobalt butyl phthalate to give a film drying at room temperature in a few days and at 110 DEG C. in 30 mins.; (c) a compound of the general formula given above in which R is <FORM:0918360/III/3> and X is <FORM:0918360/III/4> is mixed with a small amount of cobalt butyl phthalate to give a composition which is used for coating steel panels; (d) bis-(4,5-divinyl-1,3-dioxol-2-yl) benzene is mixed with toluene and cobalt butyl phthalate to give a coating composition for steel panels; and (e) the compound of formula <FORM:0918360/III/5> is mixed with 1% of cobalt butyl phthalate and used as a coating composition for panels.ALSO:The invention comprises bis-1,3-dioxolanes of the formula <FORM:0918360/IV (b)/1> in which R is a tetravalent organic radical having at least 2 carbon atoms, each terminal carbon atom of the radical being a member of one dioxolane ring, and X is an organic radical comprising 2 carbon atoms in the dioxolane ring, at least one of said ring carbon atoms carrying an alkenyl substituent. Preferably the terminal carbon atoms in R carry a hydrogen atom. The compounds may be prepared by reacting at least one alkenyl substituted ethylene glycol of formula HO-X-OH with at least one dialdehyde or diketone of formula O=R=O, or lower alkyl tetraacetals or ketals thereof, at a temperature of 50-150 DEG C. in the presence of an acidic catalyst. Suitable alkenyl substituted glycols are, for example, 1,2-divinyl; 1,2-diisopropenyl-; 1,2-di-(a -isopropylvinyl)-; 1,2 - dipropenyl-; 1,2 - divinyl - 1,2-dimethyl-; 1,2 - dibut - 11 - enyl-; 1,2-dipent-11-enyl-; 1,2-di-(hepta-1,3,5-trienyl)-; 1,2-dihex-11-enyl-; 1,2-dihept-11-enyl-; 1,2-diphenyl-1,2-divinyl-; 1,2 - dithenyl - 1,2 - divinyl-; 1-vinyl-2-thenyl-; 1,2-di-(2-methylpropen-1-yl)-; 1-vinyl-; 1-vinyl-2-cyclohexyl-; 1-isopropenyl-; 1-furyl-2 - vinyl-; and 1,1-divinyl-2-furfuryl-ethylene glycol.  Suitable aldehydes, ketones, acetals and ketals are glyoxal; glutaraldehyde; adipaldehyde; terephthaldehyde; 2,5-furan-diol; oxybis-(5-methylene-2-furfuraldehyde); 2,5-furandi-(3-propional); 1,2-di-(6-formyl-2-tetrahydro-pyranoxy)ethane; 2,2-bis[p-6-formyl - 2 - tetrahydropyranoxy)-phenyl]propane; dodecane-1, 12-diol; 1,1,3,3-tetraethoxy propane; 1,1,3-trimethoxy-3-ethoxy propane; suberic dialdehyde tetraethyl acetal; 1,1,4,4-tetraethoxy ethane; 1,1,7,7-tetraethoxy-hept-3,4-ene; 2,2,5,5-tetraethoxyfuran; cyclohexane - 1,6 - dione; acetonyl acetone; 1,3-diphenyl-1,3-propane-dione; 1,4-dimethyl-1,1,4,4-tetraethoxy butane and 1,8-diethyl-1,1,8,8-tetramethoxy octane.  Suitable catalysts are, for example, strong mineral acids, which may be deposited on silica-alumina carriers, or organic acids. Stablizers, e.g. hydroquinone or tertiary butyl catechol, may be added to the reaction mixture.  Examples are given of the preparation of various of the new compounds and it is stated that bis-[4-(a -chlorovinyl)-5-vinyl-1,3-dioxol-2-yl]methane may be prepared in a similar manner.  2,2 - Bis - [p-(6-formyl-2-tetrahydropyranoxy) phenyl]-propane used as starting material in Example 5 is prepared by reacting 2,2-bis-(41-hydroxyphenyl)propane with bisacrolein.